US8299282B2 - Continuous method for the heterogenically catalyzed esterification of fatty acids - Google Patents

Continuous method for the heterogenically catalyzed esterification of fatty acids Download PDF

Info

Publication number
US8299282B2
US8299282B2 US12/738,115 US73811508A US8299282B2 US 8299282 B2 US8299282 B2 US 8299282B2 US 73811508 A US73811508 A US 73811508A US 8299282 B2 US8299282 B2 US 8299282B2
Authority
US
United States
Prior art keywords
process according
fatty acids
free fatty
catalyst
alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related, expires
Application number
US12/738,115
Other languages
English (en)
Other versions
US20100249442A1 (en
Inventor
Dieter Heinz
Leslaw Mleczko
Shaibal Roy
Heinrich Morhenn
Wulf Dietrich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rohm and Haas Chemicals LLC
Original Assignee
Bayer Technology Services GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Technology Services GmbH filed Critical Bayer Technology Services GmbH
Assigned to BAYER TECHNOLOGY SERVICES GMBH reassignment BAYER TECHNOLOGY SERVICES GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HEINZ, DIETER, DR., ROY, SHAIBAL, DR., MLECZKO, LESLAW, DR., DIETRICH, WULF, DR., MORHENN, HEINRICH, DR.
Publication of US20100249442A1 publication Critical patent/US20100249442A1/en
Application granted granted Critical
Publication of US8299282B2 publication Critical patent/US8299282B2/en
Assigned to BAYER INTELLECTUAL PROPERTY GMBH reassignment BAYER INTELLECTUAL PROPERTY GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAYER TECHNOLOGY SERVICES GMBH
Assigned to ROHM AND HAAS CHEMICALS LLC reassignment ROHM AND HAAS CHEMICALS LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAYER INTELLECTUAL PROPERTY GMBH
Expired - Fee Related legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • DE 196 00 025 discloses, inter alia, that it may be advantageous to add additional free fatty acids to the pre-esterification. Under some circumstances, this can serve to reduce the relative proportion by mass of inert material in the starting material of the process.
  • no fundamental solution to the technical problem of achieving higher conversions and consequent increased space-time yields of a pre-esterification is disclosed, since, more particularly, the free fatty acids used for the increase in the proportion of the free fatty acids preferably stem from a later process step and are therefore subjected to further processing steps. This is especially true because soap cleavage by means of metered addition of homogeneously dissolved acids becomes necessary here.
  • the maximum space-time yield disclosed in DE 196 00 025 is 34 g of fatty acid methyl ester per litre of reactor volume and hour.
  • starting materials are all fats and/or oils which include at least a proportion of free fatty acids, and a proportion of fatty acid glycerides. Preference is given to starting materials which possess a proportion of free fatty acids greater than 2% by weight.
  • alcohols refer to mono- or polyhydric C 1 to C 5 alcohols or mixtures thereof Preference is given to monohydric C 1 to C 3 alcohols. Very particular preference is given to methanol.
  • the hydricity of an alcohol describes the number of covalently bonded hydroxyl groups present in the inventive alcohol.
  • the conversion of free fatty acids at the outlet of the second reaction stage is at least 90% based on the stream from the first reaction stage ( 5 ) and at least 99.5% based on the stream into the first reaction stage ( 3 ).
  • the stream ( 9 ) of the free fatty acids which have thus been converted to alkyl esters is added, in a mixer ( 60 ), in step 6) of the process according to the invention, to the stream ( 11 ) of starting material which stems from the reaction stage ( 20 ) for transesterification and has likewise been converted to alkyl esters, so as to obtain, for example, a stream of biodiesel ( 12 ).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Fats And Perfumes (AREA)
  • Catalysts (AREA)
US12/738,115 2007-10-30 2008-10-16 Continuous method for the heterogenically catalyzed esterification of fatty acids Expired - Fee Related US8299282B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102007052065 2007-10-30
DE102007052065A DE102007052065A1 (de) 2007-10-30 2007-10-30 Kontinuierliches Verfahren zur heterogen katalysierten Veresterung von Fettsäuren
DE102007052065.6 2007-10-30
PCT/EP2008/008763 WO2009056231A1 (de) 2007-10-30 2008-10-16 Kontinuierliches verfahren zur heterogen katalysierten veresterung von fettsäuren

Publications (2)

Publication Number Publication Date
US20100249442A1 US20100249442A1 (en) 2010-09-30
US8299282B2 true US8299282B2 (en) 2012-10-30

Family

ID=40292442

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/738,115 Expired - Fee Related US8299282B2 (en) 2007-10-30 2008-10-16 Continuous method for the heterogenically catalyzed esterification of fatty acids

Country Status (22)

Country Link
US (1) US8299282B2 (OSRAM)
EP (1) EP2205708A1 (OSRAM)
CN (1) CN101842471B (OSRAM)
AR (1) AR071058A1 (OSRAM)
AU (1) AU2008318001A1 (OSRAM)
BR (1) BRPI0819144A8 (OSRAM)
CA (1) CA2703813A1 (OSRAM)
CO (1) CO6270372A2 (OSRAM)
CR (1) CR11400A (OSRAM)
DE (1) DE102007052065A1 (OSRAM)
EA (1) EA018797B1 (OSRAM)
HN (1) HN2010000893A (OSRAM)
IL (1) IL204938A (OSRAM)
MX (1) MX2010004519A (OSRAM)
NI (1) NI201000073A (OSRAM)
NZ (1) NZ584970A (OSRAM)
PA (1) PA8799301A1 (OSRAM)
PE (1) PE20090934A1 (OSRAM)
SV (1) SV2010003551A (OSRAM)
UY (1) UY31390A1 (OSRAM)
WO (1) WO2009056231A1 (OSRAM)
ZA (1) ZA201002942B (OSRAM)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8957242B2 (en) 2013-03-15 2015-02-17 Renewable Energy Group, Inc. Dual catalyst esterification

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2522712A1 (en) * 2011-05-13 2012-11-14 Cognis IP Management GmbH Process for obtaining fatty acid lower alkyl esters from unrefined fats and oils
US9738842B2 (en) * 2013-06-19 2017-08-22 Argent Energy (Uk) Limited Process and apparatus for purifying a fatty mixture and related products including fuels
FR3015515B1 (fr) 2013-12-19 2016-02-05 IFP Energies Nouvelles Procede de pretraitement d'huiles vegetales par catalyse heterogene de l'esterification des acides gras

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB384715A (en) * 1931-08-31 1932-12-15 Ig Farbenindustrie Ag Apparatus for carrying out the manufacture and production of neutral products from oiats
DE1960002A1 (de) 1968-12-04 1970-06-18 Jean Joseph Alfred Beyl Sicherheitsskibindung
GB2145079A (en) * 1983-08-17 1985-03-20 Nisshin Oil Mills Ltd Methyl-esterification of deodorisation distillates of oils
EP0192035A2 (de) 1985-01-21 1986-08-27 Henkel Kommanditgesellschaft auf Aktien Verfahren zur Vorveresterung freier Fettsäuren in Rohfetten und/oder -ölen
DE19600025A1 (de) 1996-01-03 1997-07-10 Henkel Kgaa Verfahren zur Herstellung von Fettstoffen
US20050113589A1 (en) * 2003-10-14 2005-05-26 Kao Corporation Process for producing a fatty acid ester
WO2007083213A2 (en) 2006-01-19 2007-07-26 Merloni Progetti S.P.A. Process for the preparation of biodiesel
WO2007093326A1 (en) 2006-02-15 2007-08-23 Aser S.R.L. Method for deacidifying oils and/or fats

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1865401A (zh) * 2006-06-19 2006-11-22 菏泽华瑞油脂有限责任公司 高酸价棉籽油制取生物柴油的方法
CN101016473B (zh) * 2007-03-02 2012-04-18 安徽省粮油科学研究所 劣质油生产生物燃料油的方法
CN101058734B (zh) * 2007-05-31 2010-12-01 张付舜 工业化微波合成生物柴油的装置及其方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB384715A (en) * 1931-08-31 1932-12-15 Ig Farbenindustrie Ag Apparatus for carrying out the manufacture and production of neutral products from oiats
DE1960002A1 (de) 1968-12-04 1970-06-18 Jean Joseph Alfred Beyl Sicherheitsskibindung
GB2145079A (en) * 1983-08-17 1985-03-20 Nisshin Oil Mills Ltd Methyl-esterification of deodorisation distillates of oils
EP0192035A2 (de) 1985-01-21 1986-08-27 Henkel Kommanditgesellschaft auf Aktien Verfahren zur Vorveresterung freier Fettsäuren in Rohfetten und/oder -ölen
US4698186A (en) 1985-01-21 1987-10-06 Henkel Kommanditgesellschaft Auf Aktien Process for the pre-esterification of free fatty acids in fats and oils
DE19600025A1 (de) 1996-01-03 1997-07-10 Henkel Kgaa Verfahren zur Herstellung von Fettstoffen
US20050113589A1 (en) * 2003-10-14 2005-05-26 Kao Corporation Process for producing a fatty acid ester
WO2007083213A2 (en) 2006-01-19 2007-07-26 Merloni Progetti S.P.A. Process for the preparation of biodiesel
WO2007093326A1 (en) 2006-02-15 2007-08-23 Aser S.R.L. Method for deacidifying oils and/or fats

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Athanassiadis, A., et al., The deacidification of Vegetable oils by distillation during deodorization, 1988, Fat. Sci. Technol., vol. 90, No. 13, pp. 522-526. *
DIN EN ISO 2114 Plastics (polyester resins) and paints and varnishes (binders)-Determination of partial acid value and total acid value (ISO 2114:2000).
Henkel KGGA, Preparation of fatty acids with low acid values, useful as precursors for esterification, 1997, English translation of DE19600025, 11 pages. *
Martinello, M., et al., Grape seed oil deacidification by molecular distillation: Analysis of operative variables influence using the response surfact methodology, 2006, Journal of Food Engineering, vol. 81. pp. 60-64. *
Mittelbach, Remschmidt, Biodiesel-The comprehensive handbook 3rd ed., 2006, p. 60.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8957242B2 (en) 2013-03-15 2015-02-17 Renewable Energy Group, Inc. Dual catalyst esterification

Also Published As

Publication number Publication date
NI201000073A (es) 2010-09-23
US20100249442A1 (en) 2010-09-30
PA8799301A1 (es) 2009-06-23
PE20090934A1 (es) 2009-07-24
IL204938A (en) 2013-12-31
HN2010000893A (es) 2013-06-24
CN101842471B (zh) 2014-12-10
ZA201002942B (en) 2011-07-27
EP2205708A1 (de) 2010-07-14
BRPI0819144A8 (pt) 2016-04-26
BRPI0819144A2 (OSRAM) 2009-05-07
AU2008318001A1 (en) 2009-05-07
DE102007052065A1 (de) 2009-05-07
EA018797B1 (ru) 2013-10-30
CN101842471A (zh) 2010-09-22
CA2703813A1 (en) 2009-05-07
AR071058A1 (es) 2010-05-26
UY31390A1 (es) 2009-05-29
WO2009056231A1 (de) 2009-05-07
CR11400A (es) 2010-11-02
NZ584970A (en) 2012-06-29
CO6270372A2 (es) 2011-04-20
SV2010003551A (es) 2011-08-11
MX2010004519A (es) 2010-05-14
EA201000582A1 (ru) 2010-10-29
IL204938A0 (en) 2010-11-30

Similar Documents

Publication Publication Date Title
US4698186A (en) Process for the pre-esterification of free fatty acids in fats and oils
EP2697348B1 (en) A process for autocatalytic esterification of fatty acids
EA004051B1 (ru) Способ получения жирнокислотных эфиров одновалентных алкиловых спиртов и его применение
JP2000109883A (ja) 油脂類から脂肪酸のアルキルエステルを製造する方法
CA2615712C (en) Method for production of carboxylic alkyl esters
JP2005350632A (ja) バイオディーゼル燃料の製造方法
US8299282B2 (en) Continuous method for the heterogenically catalyzed esterification of fatty acids
US20110092725A1 (en) Catalysis Of Fats And Oils To Alkyl Esters Using Hydrolysis As Pretreatment
EP1512738A1 (en) Process for producing fatty acid alkyl ester composition
US20120245398A1 (en) Process for the purification of crude glycerol
JP2005126346A (ja) 油脂類からの脂肪酸低級アルキルエステルの製造方法
JP2005350631A (ja) 酸性油脂類および劣化油脂類からのバイオディーゼル燃料製造方法
US20100048941A1 (en) Biodiesel process and catalyst therefor
US11851403B1 (en) Processes and systems for improved alkyl ester production from feedstocks containing organic acids using low pressure alkylation
JP2009120847A (ja) バイオディーゼル燃料の製造方法
HK1148552A (en) Continuous method for the heterogenically catalyzed esterification of fatty acids
US20100126060A1 (en) Biodiesel production with reduced water emissions
JP2009161776A (ja) バイオディーゼル燃料の製造方法及び製造装置
JPWO2006016492A1 (ja) バイオディーゼル燃料用組成物の製造方法およびバイオディーゼル燃料製造装置
JP7417271B2 (ja) ポリ乳酸の製造方法
US20120288906A1 (en) Process For Obtaining Fatty Acid Lower Alkyl Esters From Unrefined Fats And Oils
EP2522712A1 (en) Process for obtaining fatty acid lower alkyl esters from unrefined fats and oils
PL216247B1 (pl) Sposób oczyszczania fazy estrowej z procesu transestryfikacji trójglicerydów tłuszczowych niskocząsteczkowymi alkoholami alifatycznymi
JPH051021A (ja) α−スルホ脂肪酸エステルの製造法
WO2000075096A1 (en) Process for the reduction of glycerin in transesterification operations

Legal Events

Date Code Title Description
AS Assignment

Owner name: BAYER TECHNOLOGY SERVICES GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HEINZ, DIETER, DR.;MLECZKO, LESLAW, DR.;ROY, SHAIBAL, DR.;AND OTHERS;SIGNING DATES FROM 20100414 TO 20100507;REEL/FRAME:024428/0276

STCF Information on status: patent grant

Free format text: PATENTED CASE

AS Assignment

Owner name: BAYER INTELLECTUAL PROPERTY GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BAYER TECHNOLOGY SERVICES GMBH;REEL/FRAME:031157/0347

Effective date: 20130812

AS Assignment

Owner name: ROHM AND HAAS CHEMICALS LLC, PENNSYLVANIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BAYER INTELLECTUAL PROPERTY GMBH;REEL/FRAME:032652/0667

Effective date: 20140401

FPAY Fee payment

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

LAPS Lapse for failure to pay maintenance fees

Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20201030